CN108379581A - A kind of ferroso-ferric oxide-carbon-gold pharmaceutical carrier and preparation method thereof - Google Patents

A kind of ferroso-ferric oxide-carbon-gold pharmaceutical carrier and preparation method thereof Download PDF

Info

Publication number
CN108379581A
CN108379581A CN201810297722.6A CN201810297722A CN108379581A CN 108379581 A CN108379581 A CN 108379581A CN 201810297722 A CN201810297722 A CN 201810297722A CN 108379581 A CN108379581 A CN 108379581A
Authority
CN
China
Prior art keywords
ferroso
ferric oxide
carbon
pharmaceutical carrier
gold
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201810297722.6A
Other languages
Chinese (zh)
Inventor
高濂
冯效迁
张扬
张鹏
宋雪峰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Jiaotong University
Shanghai Tenth Peoples Hospital
Original Assignee
Shanghai Jiaotong University
Shanghai Tenth Peoples Hospital
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Jiaotong University, Shanghai Tenth Peoples Hospital filed Critical Shanghai Jiaotong University
Priority to CN201810297722.6A priority Critical patent/CN108379581A/en
Publication of CN108379581A publication Critical patent/CN108379581A/en
Pending legal-status Critical Current

Links

Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K41/00Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
    • A61K41/0052Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/02Inorganic compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y5/00Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Biophysics (AREA)
  • Biotechnology (AREA)
  • General Engineering & Computer Science (AREA)
  • Medical Informatics (AREA)
  • Molecular Biology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)

Abstract

The invention discloses a kind of ferroso-ferric oxide carbon gold pharmaceutical carriers and preparation method thereof.In the pharmaceutical carrier, ferroso-ferric oxide core is coated by spherical carbon shell, and there are larger space among carbon shell, nanogold particle is carried on carbon shell surface.Preparation method:Monodisperse ferriferrous oxide particles are prepared by coprecipitation under sodium citrate auxiliary using iron chloride and frerrous chloride first, it is then act through tetraethyl orthosilicate and is coated on its surface cladding layer of silicon dioxide, reuse formaldehyde resorcinol copolymer and coat one layer of carbon.Using naoh treatment to remove silica template, finally by infusion process by gold-nanoparticle-supported in the pharmaceutical carrier on carbon shell, just obtaining the present invention.Pharmaceutical carrier produced by the present invention has the excellent performances such as good chemical stability, biocompatibility, magnetism characteristic and photo-thermal therapy characteristic, and the pharmaceutical carrier synthesis temperature prepared by the present invention is low, environmental-friendly, can be mass-produced.

Description

A kind of ferroso-ferric oxide-carbon-gold pharmaceutical carrier and preparation method thereof
Technical field
The present invention relates to a kind of drug carrier material more particularly to a kind of carbon-based drug carrier materials, belong to pharmaceutical carrier Preparation field.
Background technology
In recent years, medical technology continues to develop, and the medical demand of the mankind is growing, and traditional direct administration mode is more next More it is restricted.Although many drugs have good therapeutic effect to lesions position, also human body can be greatly being damaged just simultaneously Often tissue and organ.And with the progress of nanotechnology, nano-medicament carrier has progressed into the visual field of researcher.Pass through target To pharmaceutical carrier, drug can be oriented and be transported to active component, greatly improve its curative effect, and reduce side effect.
In many pharmaceutical carriers, carbon-based pharmaceutical carrier because it is with good chemical stability and biocompatibility, from And it is widely paid close attention to.Relative to one-dimensional carbon nanotube and two-dimensional graphene, three-dimensional nano-hollow carbon ball has most Big Drug loading capacity is also very beneficial to the compound structure for new residence of other functional materials of design (calculated) load on its basis, to obtain More functional characteristics reach more excellent therapeutic effect.Wherein magnetism characteristic and photo-thermal therapy characteristic is that application is the widest General functional characteristic.As Applied Materials&Interface magazines the 8th 14470-14480 pages of the phase in 2016 reports The pharmaceutical carrier of ferroso-ferric oxide is loaded, and therefore obtains good magnetism characteristic.7th 4354-4367 pages of the phase in 2015 is then The pharmaceutical carrier for reporting while loading ferroso-ferric oxide and nanogold particle obtains excellent magnetism characteristic and photo-thermal therapy Characteristic.These are research shows that the extensive use of ferroso-ferric oxide and nanogold in pharmaceutical carrier field, by itself and carbon-based medicine The progress of object carrier is compound, then can obtain having good chemical stability, biocompatibility, magnetism characteristic and photo-thermal therapy special The pharmaceutical carrier of the excellent performances such as property.
Therefore, researcher of the invention is dedicated to designing and synthesizing a kind of ferroso-ferric oxide-carbon-with multiple functions Golden pharmaceutical carrier.
Invention content
In view of the defect of the prior art, the problem to be solved in the present invention is a kind of four oxidations three with multiple functions of design Iron-carbon-gold pharmaceutical carrier and offer and preparation method thereof.
To obtain the pharmaceutical carrier of the function admirable with multiple functions characteristic as described above, the present invention provides one kind Ferroso-ferric oxide-carbon-gold pharmaceutical carrier and preparation method thereof, which is characterized in that include the following steps:
Step 1, iron chloride, frerrous chloride are dissolved in the burning for filling the deionized water by argon gas deoxidation at room temperature In cup, sodium hydroxide solution is added into beaker under mechanical stirring, beaker is placed on after stirring 0.5-5h on magnetic stirring apparatus, Beaker water-bath is heated to 60-120 DEG C of stirring 0.5-5h, products therefrom is collected with magnet, product is scattered in and fills citric acid In the beaker of sodium solution, beaker water-bath is heated to 60-120 DEG C of stirring 0.5-5h, products therefrom is collected with magnet again and is used in combination Acetone cleans, and is scattered in deionized water after product is dried under vacuum, dialysis treatment to a certain concentration obtains four oxygen Change three-iron dispersion liquid;
Step 2, tetraethyl orthosilicate is dissolved in ethyl alcohol and obtains tetraethyl orthosilicate dispersion liquid, ferroso-ferric oxide is disperseed Liquid and ammonium hydroxide are added in the beaker for the mixed solution for filling water and ethyl alcohol, and it is uniform that beaker is placed on ultrasonic mixing in Ultrasound Instrument, so Tetraethyl orthosilicate dispersion liquid is added in backward beaker, stirs 4-20h, centrifuge products therefrom and is washed several times with ethanol Afterwards, obtained solid product is distributed in the beaker for filling methanol solution, 3- aminopropyl-triethoxy silicon is added into beaker Alkane, stirs 1-6h, and reaction terminates;
Step 3, dry after step 2 reaction product is collected by centrifugation and is washed several times with ethanol, it is added into and fills water and second In the beaker of the mixed solution of alcohol, ammonium hydroxide, resorcinol and formaldehyde are then sequentially added, 1-6h is stirred at 20-60 DEG C, is reacted Terminate;
Step 4, step 3 reaction product is collected by centrifugation and is cleaned with ethyl alcohol and deionized water and dries afterwards for several times, is produced dry Object is transferred in Muffle furnace, is heated to 600-900 DEG C of calcining 2-6h under protection of argon gas, is added that fill sodium hydroxide molten after cooling In the beaker of liquid, by beaker water-bath be heated to 40-80 DEG C stirring 10-30h after dialyse, be centrifugally separating to obtain solid product and by its It is dry;
Step 5, ethylenediamine is added in chlorauric acid solution and obtains reaction solution, it will be dry obtained by reaction solution and step 4 Product is added in deionized water, is centrifugally separating to obtain solid product after stirring 2-10h and is transferred in Muffle furnace after being dried, In the hydrogen-argon mixed atmosphere containing 5% hydrogen, 0.5-4h is calcined at 150-350 DEG C, obtains ferroso-ferric oxide-carbon-gold Pharmaceutical carrier.
Further, in step 1, the iron chloride and its molar ratio of the frerrous chloride are 2:1, the deionized water Molar ratio with the frerrous chloride is 200:1~2000:1, the concentration of sodium hydroxide solution is 10mol/L, the hydrogen The molar ratio of sodium oxide molybdena and the frerrous chloride is 6:1~12:1, a concentration of 0.1mol/L of sodium citrate solution~ 1.0mol/L。
Further, in step 2, the volume ratio of the ethyl orthosilicate and the ethyl alcohol is 1:50~1:5, the water and The volume ratio of the ethyl alcohol is 1:2~1:6, the ethyl orthosilicate dispersion liquid, ammonium hydroxide, ferroso-ferric oxide dispersion liquid, water and second The volume ratio of mixed alkoxide solution is 15~25:2~4:1~3:160, the mass ratio of the solid product and methanol solution is 1:40 ~1:100, the volume ratio of the 3- aminopropyl triethoxysilanes and methanol solution is 1:100~1:600.
Further, in step 3, the volume ratio of the water and ethyl alcohol is 1:0.5~1:5, the reaction product, ammonia The mass ratio of water, resorcinol, formaldehyde and water and alcohol mixed solution is 1:1:1:1:100~500.
Further, in step 4, a concentration of 0.5-4mol/L of the sodium hydroxide solution.
Further, in step 5, a concentration of 10mg/mL of chlorauric acid solution, the ethylenediamine and the gold chloride are molten The volume ratio of liquid is 1:50~1:400, the mass ratio of the reaction product, the mixed solution and the deionized water is 1:10 ~50:200~600.
Further, ferroso-ferric oxide-carbon-gold medicine obtained by a kind of preparation method of ferroso-ferric oxide-carbon-gold pharmaceutical carrier Object carrier, the ferroso-ferric oxide-carbon-gold pharmaceutical carrier, including ferroso-ferric oxide core, spherical carbon shell and nanogold particle.
Further, the ferroso-ferric oxide core is spherical shape, is coated by the spherical carbon shell, among the spherical shape carbon shell There are larger space, the nanogold particle is carried on carbon shell surface.
Further, the ferroso-ferric oxide core is crystalline state ferroso-ferric oxide, and the spherical shape carbon shell is unformed shape, described Nanogold particle is crystalline state gold.
Further, the internal diameter of a diameter of 10nm of the ferroso-ferric oxide core, the spherical shape carbon shell are 80nm, and thickness is The grain size of 10nm, the nanogold particle are 4nm.
The advantage of the present invention compared with the prior art is that carbon-based pharmaceutical carrier prepared by the present invention is one kind by nanometer four The composite construction that Fe 3 O particle, nano-hollow carbon ball and nanogold particle are formed, wherein ferriferrous oxide particles are wrapped It is overlying on inside nano-hollow carbon ball, there is larger space, nanogold particle to be carried on carbon ball surface therebetween.This structure Benefit is that space larger inside nano-hollow carbon ball provides outstanding Drug loading capacity, and ferriferrous oxide particles provide outstanding Magnetic responsiveness energy, nanogold particle then provides good photo-thermal therapy performance.Secondly, this material prepared by the present invention Synthesis temperature is low, environmental-friendly, can be mass-produced.
The technique effect of the design of the present invention, concrete structure and generation is described further below with reference to attached drawing, with Fully understand the purpose of the present invention, feature and effect.
Description of the drawings
Fig. 1 is the TEM photos for ferroso-ferric oxide-carbon-gold pharmaceutical carrier that the preferred embodiment 1 of the present invention obtains;
Fig. 2 is that the X-ray for ferroso-ferric oxide-carbon-gold pharmaceutical carrier that the preferred embodiment 1 of the present invention obtains is spread out Penetrate collection of illustrative plates;
Fig. 3 is the hysteresis loop for ferroso-ferric oxide-carbon-gold pharmaceutical carrier that the preferred embodiment 1 of the present invention obtains;
Fig. 4 is the hysteresis loop for ferroso-ferric oxide-carbon-gold pharmaceutical carrier that the example 2 of the present invention obtains.
Specific implementation mode
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Range.
Embodiment 1
Sodium hydroxide is dissolved in magnetic agitation 10 minutes in deionized water, is made into the solution of a concentration of 0.4g/mL, it will 10g Iron(III) chloride hexahydrates and 4g Iron dichloride tetrahydrates are dissolved in the deionized water that 150mL argon-degasseds are crossed, in high speed machine The above-mentioned sodium hydroxide solutions of 20mL are added dropwise in 30 minutes under tool stirring, stirs 1 hour at room temperature, then raises temperature to 90 DEG C, it is stirred for 1 hour.Sodium citrate is dissolved in deionized water, magnetic agitation 10 minutes obtains the solution of 150mg/mL. To the end of reaction, magnet collecting reaction product is used after being cooled to room temperature, then product is dispersed to the above-mentioned sodium citrate solutions of 200mL In, it is heated to after keeping the temperature 1 hour at 80 DEG C, collects product with magnet again, be dried in vacuo at 30 DEG C, then again by desciccate It is dispersed in 50mL deionized waters, dialysis removes extra citrate ion to get to ferroso-ferric oxide suspension, is adjusted It is whole to mass fraction be 2%.It suspends to 2mL ferroso-ferric oxides are added in the mixed solution of 120mL deionized waters and 40mL ethyl alcohol Liquid and 3mL ammonium hydroxide, ultrasonic disperse are uniform.Tetraethyl orthosilicate is dissolved in ethyl alcohol, stirs 10 minutes, obtains 30mg/mL's Solution, by 20mL, the solution is added dropwise in ferroso-ferric oxide mixed solution, mechanical agitation 12 hours.After reaction, it centrifuges Isolated product is simultaneously washed 2 times with ethyl alcohol, then product is dispersed in 10mL methanol, and 300 μ l 3- aminopropyls are added thereto Triethoxysilane, stirring are centrifugally separating to obtain product after 3 hours, twice and are dried with ethyl alcohol wash products.It is dry by what is obtained Dry product ultrasonic disperse sequentially adds 0.1g ammonium hydroxide thereto in 20mL ethyl alcohol and the mixed solution of 10mL deionized waters, 0.1g resorcinols and 0.1g formaldehyde stir 3 hours at 30 DEG C, are centrifugally separating to obtain product after reaction, use deionization Water and each wash products of ethyl alcohol are dried afterwards twice, and desciccate is transferred in Muffle furnace, in argon gas atmosphere, are forged at 650 DEG C It burns 4 hours, product is added in sodium hydroxide solution after cooling, is stirred 24 hours at 50 DEG C, then dialyses, is centrifugally separating to obtain Solid product and drying.100 μ l ethylenediamines are added in 10mL 10mg/mL chlorauric acid solutions, stirring obtains reacting molten for 10 minutes The above-mentioned products of 600 μ l and reaction solution are added in 5mL deionized waters liquid, stir 5 hours, are centrifugally separating to obtain solid product And it is dry, desciccate is transferred in Muffle furnace, in the hydrogen-argon-mixed atmosphere containing 5% hydrogen, 1 is calcined at 200 DEG C Hour to get to final product ferroso-ferric oxide-carbon-gold pharmaceutical carrier.
Embodiment 2:
Sodium hydroxide is dissolved in magnetic agitation 10 minutes in deionized water, is made into the solution of 0.4g/mL, by six water of 10g It closes ferric trichloride and 4g Iron dichloride tetrahydrates is dissolved in the deionized water that 150mL argon-degasseds are crossed, stirred in high speed machine Under the above-mentioned sodium hydroxide solutions of 20mL are added dropwise in 30 minutes, at room temperature stir 1 hour, then raise temperature to 90 DEG C, then stir It mixes 1 hour.Sodium citrate is dissolved in deionized water, magnetic agitation 10 minutes obtains the solution of 150mg/mL.Wait for reaction knot Beam uses magnet collecting reaction product, then product is dispersed in the above-mentioned sodium citrate solutions of 200mL after being cooled to room temperature, heat After keeping the temperature 1 hour to 80 DEG C, product is collected with magnet again, is dried in vacuo at 30 DEG C, is then again dispersed to desciccate In 50mL deionized waters, dialysis removes extra citrate ion to get to ferroso-ferric oxide suspension, is adjusted to matter It is 2% to measure score.To addition 2mL ferroso-ferric oxides suspension and 3mL in the mixed solution of 120mL deionized waters and 40mL ethyl alcohol Ammonium hydroxide, ultrasonic disperse are uniform.Tetraethyl orthosilicate is dissolved in ethyl alcohol, stirs 10 minutes, obtains the solution of 30mg/mL, it will The 20mL solution is added dropwise in ferroso-ferric oxide mixed solution, mechanical agitation 12 hours.After reaction, it is centrifugally separating to obtain Product is simultaneously washed 2 times with ethyl alcohol, then product is dispersed in 10mL methanol, and 300 μ l 3- aminopropyl-triethoxies are added thereto Silane, stirring are centrifugally separating to obtain product after 3 hours, are cleaned twice and dried with ethyl alcohol.By obtained product ultrasonic disperse in In 20mL ethyl alcohol and the mixed solution of 10mL deionized waters, 0.1g ammonium hydroxide, 0.1g resorcinols and 0.1g are sequentially added thereto Formaldehyde stirs 3 hours at 30 DEG C.It is centrifugally separating to obtain product after reaction, with deionized water and each wash products of ethyl alcohol It dries afterwards twice, desciccate is transferred in Muffle furnace, in argon gas atmosphere, calcined 4 hours at 800 DEG C, it will production after cooling Object is added in sodium hydroxide solution, is stirred 24 hours at 50 DEG C, then dialyses, is centrifugally separating to obtain solid product and drying.It will 100 μ l ethylenediamines, which are added in 10mL 10mg/mL chlorauric acid solutions to stir 10 minutes, obtains reaction solution, by the 600 above-mentioned products of μ l It is added in 5mL deionized waters with reaction solution, stirs 5 hours, be centrifugally separating to obtain solid product and drying, desciccate is turned It moves in Muffle furnace, in the hydrogen-argon-mixed atmosphere containing 5% hydrogen, 1 hour is calcined at 200 DEG C to get to final product four Fe 3 O-carbon-gold pharmaceutical carrier.
After obtaining final product ferroso-ferric oxide-carbon-gold pharmaceutical carrier, it is tested and is characterized, such as Fig. 1, this hair Shown in the TEM photos for ferroso-ferric oxide-carbon-gold pharmaceutical carrier that a bright preferred embodiment 1 obtains, under 50nm sizes, Ferroso-ferric oxide-carbon-gold pharmaceutical carrier is ideal hollow ball structure, including ferroso-ferric oxide core, spherical carbon shell and nanogold Particle, ferroso-ferric oxide core are spherical shape, are coated by spherical carbon shell, there are larger space, nanogold particles among spherical carbon shell It is carried on carbon shell surface.A diameter of 80nm of hollow ball, thickness 10nm, a diameter of 10nm of ferroso-ferric oxide nuclear particle, nanometer The a diameter of 4nm of gold particle.Such as Fig. 2, of the invention preferred embodiment 1 ferroso-ferric oxide-carbon-gold pharmaceutical carrier obtained Shown in X-ray diffracting spectrum, it is 30 °, 36 °, 43 °, 53.5 °, 57.5 ° 63.5 ° in the angle of diffraction and nearby ferroso-ferric oxide occurs Diffraction maximum, the angle of diffraction be 38 °, 45 °, 65 °, 78 ° nearby occur gold diffraction maximums, this shows ferroso-ferric oxide-carbon-gold Gold and ferroso-ferric oxide in pharmaceutical carrier are crystalline state.Four oxidations obtained such as Fig. 3, of the invention preferred embodiment 1 It shown in the hysteresis loop figure of three-iron-carbon-gold pharmaceutical carrier, is calculated, the saturation magnetization of pharmaceutical carrier is 9.30emu/ G, under the conditions of embodiment 1, ferroso-ferric oxide shows good magnetic performance in ferroso-ferric oxide-carbon-gold pharmaceutical carrier. Such as Fig. 4, the embodiment of the present invention 2 constitutes comparative example with embodiment 1, ferroso-ferric oxide-carbon-gold pharmaceutical carrier of acquisition It shown in hysteresis loop figure, is calculated, the saturation magnetization of pharmaceutical carrier is only 6.11emu/g, and it is strong to analyze its saturated magnetization Degree decrease reason is since excessively high calcination temperature makes the magnetic of ferroso-ferric oxide subside.
The preferred embodiment of the present invention has been described in detail above.It should be appreciated that those skilled in the art without It needs creative work according to the present invention can conceive and makes many modifications and variations, therefore all technician in the art Pass through the available technology of logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea Scheme, all should be in the protection domain being defined in the patent claims.

Claims (10)

1. a kind of preparation method of ferroso-ferric oxide-carbon-gold pharmaceutical carrier, which is characterized in that include the following steps:
Step 1, iron chloride, frerrous chloride are dissolved in the beaker for filling the deionized water by argon gas deoxidation at room temperature In, sodium hydroxide solution is added into beaker under mechanical stirring, then beaker is placed on magnetic stirring apparatus and stirs 0.5-5h Afterwards, beaker water-bath is heated to 60-120 DEG C of stirring 0.5-5h, collects products therefrom with magnet, product is scattered in and fills lemon In the beaker of acid sodium solution, beaker water-bath is heated to 60-120 DEG C of stirring 0.5-5h, collects products therefrom simultaneously with magnet again It is cleaned with acetone, is scattered in deionized water after product is dried under vacuum, dialysis treatment obtains ferroso-ferric oxide point Dispersion liquid;
Step 2, tetraethyl orthosilicate is dissolved in ethyl alcohol and obtains tetraethyl orthosilicate dispersion liquid, by ferroso-ferric oxide dispersion liquid and Ammonium hydroxide is added in the beaker for the mixed solution for filling water and ethyl alcohol, and it is uniform that beaker is placed on ultrasonic mixing in Ultrasound Instrument, then to Tetraethyl orthosilicate dispersion liquid is added in beaker, stirs 4-20h, it, will after centrifuging products therefrom and being washed several times with ethanol Obtained solid product is distributed in the beaker for filling methanol solution, and 3- aminopropyl triethoxysilanes, stirring are added into beaker 1-6h, reaction terminate;
Step 3, dry after step 2 reaction product is collected by centrifugation and is washed several times with ethanol, it is added into and fills water and ethyl alcohol In the beaker of mixed solution, ammonium hydroxide, resorcinol and formaldehyde are then sequentially added, 1-6h, reaction knot are stirred at 20-60 DEG C Beam;
Step 4, step 3 reaction product is collected by centrifugation and is cleaned with ethyl alcohol and deionized water and dries afterwards for several times, desciccate is turned It moves in Muffle furnace, 600-900 DEG C of calcining 2-6h is heated under argon atmosphere protection, be added that fill sodium hydroxide molten after cooling In the beaker of liquid, dialyses after heating water bath to 40-80 DEG C of stirring 10-30h, is centrifugally separating to obtain solid product and is dried;
Step 5, ethylenediamine is added in chlorauric acid solution and obtains reaction solution, by reaction solution and step 4 gained desciccate Be added in deionized water, be centrifugally separating to obtain solid product after stirring 2-10h and be transferred in Muffle furnace after being dried, containing Have in the hydrogen-argon mixed atmosphere of 5% hydrogen, 0.5-4h is calcined at 150-350 DEG C, obtains ferroso-ferric oxide-carbon-gold drug Carrier.
2. a kind of preparation method of ferroso-ferric oxide-carbon-gold pharmaceutical carrier as described in claim 1, which is characterized in that step In 1, the iron chloride and its molar ratio of the frerrous chloride are 2:1, mole of the deionized water and the frerrous chloride Than being 200:1~2000:1, the concentration of sodium hydroxide solution is 10mol/L, the sodium hydroxide and the frerrous chloride Molar ratio be 6:1~12:1, a concentration of 0.1mol/L~1.0mol/L of sodium citrate solution.
3. a kind of preparation method of ferroso-ferric oxide-carbon-gold pharmaceutical carrier as described in claim 1, which is characterized in that step In 2, the volume ratio of the ethyl orthosilicate and the ethyl alcohol is 1:50~1:5, the volume ratio of the water and ethyl alcohol is 1:2~1: 6, the ethyl orthosilicate dispersion liquid, ammonium hydroxide, ferroso-ferric oxide dispersion liquid, water and alcohol mixed solution volume ratio be 15~ 25:2~4:1~3:160, the mass ratio of the solid product and methanol solution is 1:40~1:100, three second of 3- aminopropyls Oxysilane and the volume ratio of methanol solution are 1:100~1:600.
4. a kind of preparation method of ferroso-ferric oxide-carbon-gold pharmaceutical carrier as described in claim 1, which is characterized in that step In 3, the volume ratio of the water and ethyl alcohol is 1:0.5~1:5, the reaction product, ammonium hydroxide, resorcinol, formaldehyde and water and second The mass ratio of mixed alkoxide solution is 1:1:1:1:100~500.
5. a kind of preparation method of ferroso-ferric oxide-carbon-gold pharmaceutical carrier as described in claim 1, which is characterized in that step In 4, a concentration of 0.5-4mol/L of the sodium hydroxide solution.
6. a kind of preparation method of ferroso-ferric oxide-carbon-gold pharmaceutical carrier as described in claim 1, which is characterized in that step In 5, the volume ratio of a concentration of 10mg/mL of chlorauric acid solution, the ethylenediamine and the chlorauric acid solution are 1:50~1: 400, the mass ratio of the reaction product, the mixed solution and the deionized water is 1:10~50:200~600.
7. such as the obtained ferroso-ferric oxide-of preparation method of any one ferroso-ferric oxide-carbon-gold pharmaceutical carrier of claim 1-6 Carbon-gold pharmaceutical carrier, which is characterized in that the ferroso-ferric oxide-carbon-gold pharmaceutical carrier, including ferroso-ferric oxide core, spherical carbon Shell and nanogold particle.
8. a kind of ferroso-ferric oxide-carbon-gold pharmaceutical carrier as claimed in claim 7, which is characterized in that the ferroso-ferric oxide Core is spherical shape, is coated by the spherical carbon shell, and there are larger space, the nanogold particle loads among the spherical shape carbon shell In carbon shell surface.
9. a kind of ferroso-ferric oxide-carbon-gold pharmaceutical carrier as claimed in claim 7, which is characterized in that the ferroso-ferric oxide Core is crystalline state ferroso-ferric oxide, and the spherical shape carbon shell is unformed shape, and the nanogold particle is crystalline state gold.
10. a kind of ferroso-ferric oxide-carbon-gold pharmaceutical carrier as claimed in claim 7, which is characterized in that four oxidation three A diameter of 10nm of iron core, the internal diameter of the spherical shape carbon shell are 80nm, thickness 10nm, and the grain size of the nanogold particle is 4nm。
CN201810297722.6A 2018-03-30 2018-03-30 A kind of ferroso-ferric oxide-carbon-gold pharmaceutical carrier and preparation method thereof Pending CN108379581A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810297722.6A CN108379581A (en) 2018-03-30 2018-03-30 A kind of ferroso-ferric oxide-carbon-gold pharmaceutical carrier and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810297722.6A CN108379581A (en) 2018-03-30 2018-03-30 A kind of ferroso-ferric oxide-carbon-gold pharmaceutical carrier and preparation method thereof

Publications (1)

Publication Number Publication Date
CN108379581A true CN108379581A (en) 2018-08-10

Family

ID=63073551

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810297722.6A Pending CN108379581A (en) 2018-03-30 2018-03-30 A kind of ferroso-ferric oxide-carbon-gold pharmaceutical carrier and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108379581A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109589407A (en) * 2018-11-01 2019-04-09 暨南大学 Mesoporous ruthenium nano particle and its preparation method and application for colorectal cancer targeted therapy
CN113184915A (en) * 2021-04-23 2021-07-30 扬州工业职业技术学院 Double-shell coated ferroferric oxide nano-particles, preparation method and application thereof

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101694795A (en) * 2009-08-13 2010-04-14 苏州纳米技术与纳米仿生研究所 Preparation method of multi-pore canal nuclear shell type magnet gold compound nano-particle
CN101785997A (en) * 2010-02-09 2010-07-28 清华大学 Method for preparing activated carbon-carried nano-gold catalyst
CN102671625A (en) * 2012-05-02 2012-09-19 湖北富邦科技股份有限公司 Method for preparing graphene magnetic nanometer composite materials
CN102764618A (en) * 2012-07-09 2012-11-07 东南大学 Method for preparing three-layer core-shell structural gold magnetic nano particles
CN103714929A (en) * 2013-12-25 2014-04-09 复旦大学 Magnetic mesoporous silica composite microsphere with Yolk-Shell structure and manufacturing method thereof
CN104415741A (en) * 2013-09-10 2015-03-18 中国科学院大连化学物理研究所 Composite nanometer material with core-shell structure, preparation method and application of composite nanometer material
CN105914358A (en) * 2016-06-24 2016-08-31 扬州大学 Preparation method of yolk-eggshell structured nitrogen-doped carbon-coated Fe3O4@SnO2 magnetic nanometer box
CN107522867A (en) * 2017-08-31 2017-12-29 扬州大学 The preparation method of internal confinement growth MOFs hollow Nano carbon balls
CN107591527A (en) * 2017-08-31 2018-01-16 扬州大学 The preparation method of the hollow mesoporous carbon spheres of growth in situ petal-shaped molybdenum disulfide

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101694795A (en) * 2009-08-13 2010-04-14 苏州纳米技术与纳米仿生研究所 Preparation method of multi-pore canal nuclear shell type magnet gold compound nano-particle
CN101785997A (en) * 2010-02-09 2010-07-28 清华大学 Method for preparing activated carbon-carried nano-gold catalyst
CN102671625A (en) * 2012-05-02 2012-09-19 湖北富邦科技股份有限公司 Method for preparing graphene magnetic nanometer composite materials
CN102764618A (en) * 2012-07-09 2012-11-07 东南大学 Method for preparing three-layer core-shell structural gold magnetic nano particles
CN104415741A (en) * 2013-09-10 2015-03-18 中国科学院大连化学物理研究所 Composite nanometer material with core-shell structure, preparation method and application of composite nanometer material
CN103714929A (en) * 2013-12-25 2014-04-09 复旦大学 Magnetic mesoporous silica composite microsphere with Yolk-Shell structure and manufacturing method thereof
CN105914358A (en) * 2016-06-24 2016-08-31 扬州大学 Preparation method of yolk-eggshell structured nitrogen-doped carbon-coated Fe3O4@SnO2 magnetic nanometer box
CN107522867A (en) * 2017-08-31 2017-12-29 扬州大学 The preparation method of internal confinement growth MOFs hollow Nano carbon balls
CN107591527A (en) * 2017-08-31 2018-01-16 扬州大学 The preparation method of the hollow mesoporous carbon spheres of growth in situ petal-shaped molybdenum disulfide

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
DONG YANG ET AL: ""Controlled Synthesis of Magnetite-Silica Nanocomposites via a Seeded Sol-Gel Approach"", 《J. PHYS. CHEM. C》 *
QI ZHANG ET AL: ""Designed Synthesis of Au/Fe3O4@C Janus Nanoparticles for Dual-Modal Imaging and Actively Targeted Chemo-Photothermal Synergistic Therapy of Cancer Cells"", 《CHEM. EUR. J.》 *
WENYA CAI ET AL: ""Highly sensitive in situ monitoring of catalytic reactions by surface enhancement Raman spectroscopy on multifunctional Fe3O4/C/Au NPs"", 《NANOSCALE》 *
XIAOQIAN FENG ET AL: ""Facile synthesis of yolk-shell structured Fe3O4@C-Au nanoparticles for thermotherapic application"", 《MATERIALS LETTERS》 *
YU-MEI ZHOU ET AL: ""Yolk-type Au@Fe3O4@C nanospheres for drug delivery,MRI and two-photon fluorescence imaging"", 《DALTON TRANS》 *
朱脉勇 等: ""四氧化三铁纳米材料的制备与应用"", 《化学进展》 *
王东辉 等编著: "《纳米金催化剂及其应用》", 31 October 2006, 国防工业出版社 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109589407A (en) * 2018-11-01 2019-04-09 暨南大学 Mesoporous ruthenium nano particle and its preparation method and application for colorectal cancer targeted therapy
CN109589407B (en) * 2018-11-01 2021-09-07 暨南大学 Mesoporous ruthenium nano particle for targeted therapy of colorectal cancer and preparation method and application thereof
CN113184915A (en) * 2021-04-23 2021-07-30 扬州工业职业技术学院 Double-shell coated ferroferric oxide nano-particles, preparation method and application thereof

Similar Documents

Publication Publication Date Title
Zhu et al. One-pot template-free synthesis of monodisperse and single-crystal magnetite hollow spheres by a simple solvothermal route
Cheraghi et al. Effect of lemon juice on microstructure, phase changes, and magnetic performance of CoFe2O4 nanoparticles and their use on release of anti-cancer drugs
CN101256864B (en) Superparamagnetism mesoporous silicon dioxide composite ball and preparing method thereof
Varapragasam et al. Kirkendall growth of hollow Mn3O4 nanoparticles upon galvanic reaction of MnO with Cu2+ and evaluation as anode for lithium-ion batteries
JP2015009238A (en) Metal oxide composite including hollow core and porous shell layer and method for manufacturing the same
CN105233799A (en) Magnetic metal-organic framework material with core-shell structure and preparation method therefor
CN108379581A (en) A kind of ferroso-ferric oxide-carbon-gold pharmaceutical carrier and preparation method thereof
CN101337665A (en) Ordered porous magnetic hydroxylapatite material, preparation method thereof and applications
CN109133189A (en) The preparation method of carbon coated ferriferrous oxide nanoshell supported nano-gold particle
Liu et al. Synthesis of Janus Fe3O4&mSiO2 nanocarriers for chemo-microwave therapy of cancer cells
CN104436193B (en) Preparation method of folic acid coupled gold nano-rod/polypyrrole/ferroferric oxide multifunctional composite nano diagnosis and treatment agent
Peng et al. Multifunctional Yolk–Shell Structured Magnetic Mesoporous Polydopamine/Carbon Microspheres for Photothermal Therapy and Heterogenous Catalysis
Li et al. Liquid‐Phase Synthesis of Iron Oxide Nanostructured Materials and Their Applications
Ríos-Hurtado et al. Mechanosynthesis as a simple method to obtain a magnetic composite (activated carbon/Fe3O4) for hyperthermia treatment
CN110436529B (en) Fe for magnetic thermal therapy3O4Preparation method of nano rod material
CN109701039A (en) A kind of preparation method of liver cancer dual-target magnetic nanoparticle
Munkaila et al. Hollow structured transition metal phosphates and their applications
Shah et al. Virus-templated near-amorphous iron oxide nanotubes
CN101279769A (en) Preparation of ferromagnetic ferriferrous oxide nanometer material
CN111892039A (en) MXene and carbon nanotube composite hollow nanosphere and autocatalytic preparation method and application thereof
ur Rahman et al. Mesostructured multifunctional magnetic nanocomposites for potential applications
Zhu et al. Encapsulation of Co3O4 nanoparticles inside CeO2 nanotubes: an efficient biocatalyst for the ultrasensitive detection of ascorbic acid
Mertdinç-Ülküseven et al. Magnetic core/shell structures: A case study on the synthesis and phototoxicity/cytotoxicity tests of multilayer graphene encapsulated Fe/Fe3C nanoparticles
Banerjee et al. Shape-controlled MnO nanoparticles as T1 MRI contrast agents
CN103771533A (en) Preparation method of alpha-Fe2O3 microsphere with flower-like hierarchical structure

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20180810

RJ01 Rejection of invention patent application after publication